Abstract
The degrees of rate control enable identification of rate-controlling transition states and species during (pseudo)steady-state reaction. We demonstrate a method for identifying rate-controlling transition states and species at non(pseudo)steady-state conditions by modifiying of the definitions for degrees of rate control and sensitivities to superimpose the condition that time constants of the analytical rate function are kept constant when taking the partial derivatives of rate with respect to the rate constants/free energies. The utility of transient degrees of rate control is demonstrated for catalytic reaction networks to rationalize features of the transient rate including extrema and discontinuities.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 2556-2564 |
| Number of pages | 9 |
| Journal | ACS Catalysis |
| Volume | 10 |
| Issue number | 4 |
| DOIs | |
| State | Published - Feb 21 2020 |
Bibliographical note
Funding Information:This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant no. 00039202. This work was funded by the U.S. Department of Energy, Office of Basic Energy Science, Catalysis Science Program (Award DE-SC00019028). We also acknowledge Neil K. Razdan and Matthew J. Palys for helpful technical discussions.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
Keywords
- degree of rate control
- microkinetics
- pseudosteady-state
- sensitivity
- transient reactions